反応 #75995

反応方程式

benzyl ethanimidothioate hydrochloride

4-(3-aminophenyl)-4,5-dihydro-1,3-thiazol-2-ylamine

benzyl ethanimidothioate

→

[3-(2-amino-4,5-dihydrothiazol-4-yl)phenyl]-(1-iminoethyl)amine

収率 58.9%

溶媒

ethanol

ethanol

water

反応条件

後処理

1. 1
   workup.WAITfor 2 hours at a temperature in the region of 20° C
2. 2
   その他the reaction
3. 3
   温度after which the mixture is maintained at a temperature in the region of 45° C. for 24 hours
4. 4
   その他The reaction medium is evaporated under reduced pressure (5 kPa) at a temperature in the region of 40° C
5. 5
   その他The residue obtained
6. 6
   洗浄the solution is washed with 30 cm3 of dichloromethane
7. 7
   濃縮The aqueous solution is concentrated under the above conditions
8. 8
   その他the solid obtained
9. 9
   その他is then triturated from diethyl ether
10. 10
    ろ過filtered
11. 11
    その他air-dried
12. 12
    その他purified by chromatography at atmospheric pressure on a column of silica gel (particle size 40-63μ; mass 63 g)
13. 13
    洗浄eluting with a dichloromethane/methanol/aqueous ammonia mixture (12/3/0.5 by volume)
14. 14
    workup.ADDITIONThe fractions containing the expected product
15. 15
    その他are collected
16. 16
    その他evaporated under reduced pressure (5 kPa) at a temperature in the region of 40° C

実験手順

0.15 g of benzyl ethanimidothioate hydrochloride and then 5 cm3 of ethanol are added, under an inert atmosphere and at a temperature in the region of 0° C., to a stirred solution of 0.14 g of 4-(3-aminophenyl)-4,5-dihydro-1,3-thiazol-2-ylamine in 15 cm3 of ethanol. The mixture is stirred for 1 hour at about 0° C. and then for 2 hours at a temperature in the region of 20° C. A further 0.030 g of benzyl ethanimidothioate is added to complete the reaction, after which the mixture is maintained at a temperature in the region of 45° C. for 24 hours. The reaction medium is evaporated under reduced pressure (5 kPa) at a temperature in the region of 40° C. The residue obtained is taken up in 30 cm3 of water and the solution is washed with 30 cm3 of dichloromethane. The aqueous solution is concentrated under the above conditions and the solid obtained is then triturated from diethyl ether, filtered, air-dried and purified by chromatography at atmospheric pressure on a column of silica gel (particle size 40-63μ; mass 63 g), eluting with a dichloromethane/methanol/aqueous ammonia mixture (12/3/0.5 by volume). The fractions containing the expected product are collected. These fractions are combined and then evaporated under reduced pressure (5 kPa) at a temperature in the region of 40° C. 0.100 g of [3-(2-amino-4,5-dihydrothiazol-4-yl)phenyl]-(1-iminoethyl)amine is obtained in the form of a white solid melting at 180° C. 1H NMR spectrum (250 MHz, (CD3)2SO-d6, with addition of a few drops of CD3COOD-d4, δ in ppm): 2.28 (unres. mult.: 3H); 3.18 (dd, J=12.5 and 8.5 Hz: 1H); 3.80 (dd, J=12.5 and 8.5 Hz: 1H); 5.30 (t, J=8.5 Hz: 1H); 7.21 (broad d, J=8.5 Hz: 1H); 7.27 (broad s: 1H); 7.36 (broad d, J=8.5 Hz: 1H); 7.49 (broad t, J=8.5: Hz: 1H).

出典